WO2024019560A1 - Procédé de préparation de butadiène - Google Patents

Procédé de préparation de butadiène Download PDF

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Publication number
WO2024019560A1
WO2024019560A1 PCT/KR2023/010475 KR2023010475W WO2024019560A1 WO 2024019560 A1 WO2024019560 A1 WO 2024019560A1 KR 2023010475 W KR2023010475 W KR 2023010475W WO 2024019560 A1 WO2024019560 A1 WO 2024019560A1
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Prior art keywords
butanediol
polymer blend
temperature
thermal decomposition
pyrolysis
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PCT/KR2023/010475
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English (en)
Korean (ko)
Inventor
김시민
강동균
정우철
Original Assignee
주식회사 엘지화학
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Priority claimed from KR1020220089693A external-priority patent/KR20240012146A/ko
Priority claimed from KR1020220089692A external-priority patent/KR20240012145A/ko
Priority claimed from KR1020220121582A external-priority patent/KR20240042819A/ko
Priority claimed from KR1020220127102A external-priority patent/KR20240047721A/ko
Priority claimed from KR1020230094098A external-priority patent/KR20240012334A/ko
Application filed by 주식회사 엘지화학 filed Critical 주식회사 엘지화학
Priority to EP23843406.2A priority Critical patent/EP4382517A1/fr
Publication of WO2024019560A1 publication Critical patent/WO2024019560A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
    • C07C1/207—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms from carbonyl compounds
    • C07C1/213—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms from carbonyl compounds by splitting of esters
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D319/00—Heterocyclic compounds containing six-membered rings having two oxygen atoms as the only ring hetero atoms
    • C07D319/10—1,4-Dioxanes; Hydrogenated 1,4-dioxanes
    • C07D319/12—1,4-Dioxanes; Hydrogenated 1,4-dioxanes not condensed with other rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J11/00—Recovery or working-up of waste materials
    • C08J11/04—Recovery or working-up of waste materials of polymers
    • C08J11/10—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation
    • C08J11/12—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by dry-heat treatment only
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/14—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of germanium, tin or lead
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J11/00—Recovery or working-up of waste materials
    • C08J11/04—Recovery or working-up of waste materials of polymers
    • C08J11/10—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation
    • C08J11/16—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with inorganic material
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers

Definitions

  • the present invention relates to a method for producing butadiene by thermally decomposing polyester containing repeating units derived from 1,4-butanediol or a polymer blend containing it.
  • Plastics are inexpensive and durable materials that can be used to produce a variety of products that find use in a wide range of applications. Accordingly, the production of plastics has been increasing dramatically over the past few decades. Moreover, more than 50% of these plastics are used in single-use, disposable or short-lived products that are discarded within one year of manufacture, such as packaging, agricultural films, single-use consumer goods, etc. Additionally, due to the durability of polymers, significant amounts of plastic end up in landfills and natural habitats around the world, causing increasing environmental problems. Even biodegradable plastics can last for decades, depending on local environmental factors such as levels of UV exposure, temperature, and the presence of appropriate microorganisms.
  • PET polyethylene terephthalate
  • PET waste mainly bottles
  • PET waste mainly bottles
  • sorted, and recycled They are pressed into batches, crushed, washed, cut into flakes, melted and extruded into pellets and offered for sale.
  • these plastic recycling methods only apply to plastic articles containing only PET, requiring excessive prior sorting.
  • plastic recycling allows recovering the chemical components of the polymer.
  • the resulting monomers, after purification, can be used to re-produce plastic articles, creating a need for chemical regeneration methods to recycle the polymers.
  • the present invention is intended to provide a method for producing butadiene by thermally decomposing polyester containing a repeating unit derived from 1,4-butanediol or a polymer blend containing it.
  • a method for producing butadiene is provided by thermally decomposing polyester containing a repeating unit derived from 1,4-butanediol or a polymer blend containing the same.
  • the weight average molecular weight can be measured using gel permeation chromatography (GPC). Specifically, the polyester is dissolved in chloroform to a concentration of 2 mg/ml, then 20 ⁇ l is injected into GPC, and GPC analysis is performed at 40°C. At this time, the mobile phase of GPC uses chloroform and flows at a flow rate of 1.0 mL/min, the column uses two Agilent Mixed-Bs connected in series, and the detector uses an RI Detector. The Mw value is derived using a calibration curve formed using a polystyrene standard specimen.
  • GPC gel permeation chromatography
  • the weight average molecular weights of the polystyrene standard specimens were 2,000 g/mol, 10,000 g/mol, 30,000 g/mol, 70,000 g/mol, 200,000 g/mol, 700,000 g/mol, 2,000,000 g/mol, 4,000,000 g/mol, and 10,000,000.
  • 10,000 g/mol 10,000 g/mol
  • 30,000 g/mol 70,000 g/mol
  • 200,000 g/mol g/mol
  • 700,000 g/mol 2,000,000 g/mol
  • 4,000,000 g/mol 10,000,000.
  • Nine types of g/mol were used.
  • a polymer blend is manufactured by mechanically or chemically mixing polymers produced through monomer polymerization, and can be manufactured, for example, by compounding two or more types of polymers in a molten state.
  • a method for producing butadiene including the step of producing butadiene by thermally decomposing polyester containing a repeating unit derived from 1,4-butanediol or a polymer blend containing the same.
  • polyester containing a repeating unit derived from 1,4-butanediol or a polymer blend containing it is pyrolyzed, butadiene, a recyclable monomer, can be recovered with high purity and high yield, respectively, and thus the present invention. Completed.
  • the method for producing butadiene according to the embodiment is, prior to the step of producing butadiene by pyrolyzing the polyester containing the repeating unit derived from 1,4-butanediol or a polymer blend containing the same, the repeating unit derived from 1,4-butanediol It may further include melting the polyester containing or a polymer blend containing it. That is, before the thermal decomposition, the polyester containing the 1,4-butanediol-derived repeating unit or the polymer blend containing it can be melted.
  • the melting may be performed at a temperature of 150°C or higher and 280°C or lower.
  • the melting temperature may be 150°C or higher, 160°C or higher, 170°C or higher, 180°C or higher, and may be 280°C or lower, 270°C or lower, 260°C or lower, and 250°C or lower. If the melting temperature is too low, the polyester containing the repeating unit derived from 1,4-butanediol or the polymer blend containing it may not melt, and if the melting temperature is too high, the polyester containing the repeating unit derived from 1,4-butanediol may not melt.
  • Polyester or a polymer blend containing it is thermally decomposed without melting, which reduces the recovery rate of monomers, or there is no process to remove impurities before thermal decomposition, so a large amount of impurities may be introduced, and bumping may occur due to a rapid increase in temperature. .
  • the melting may be carried out solvent free.
  • the polyester containing the 1,4-butanediol-derived repeating unit or the polymer blend containing the same may be melted without being dissolved in the solvent.
  • no solvent other than polyester containing a repeating unit derived from 1,4-butanediol or a polymer blend containing the same is added to the reactor, and the temperature applied to the reactor is adjusted to the temperature applied to the reactor containing the repeating unit derived from 1,4-butanediol. It can be directly transferred to polyester or a polymer blend containing it and melted.
  • impurities may be formed in the process of thermally decomposing the polyester containing the repeating unit derived from 1,4-butanediol or a polymer blend containing it, and the process of removing the solvent and additional impurities A removal process may be required, which may complicate the process or require additional equipment. Additionally, side reactions may occur during the process of removing the solvent, reducing the recovery rate and purity of monomers. Additionally, there is a disadvantage in that economic efficiency is lowered due to the use of additional solvents.
  • thermal decomposition may be performed under a tin catalyst.
  • the tin catalyst is, for example, tin 2-ethylhexanoate (Tin(II) 2-ethylhexanoate), tin 2-methylhexanoate (Tin(II) 2-methylhexanoate), tin 2-propylhexanoate ( Tin(II) 2-propylhexanoate), dioctyltin dilaurate, dihexyltin dilaurate, dibutyltin dilaurate, dipropyltin dilaurate dilaurate), diethyltin dilaurate, dimetyltin dilaurate, dibutyltin bis(lauryl mercaptide), dimethyltin bis(lauryl mercaptide) Mercaptide) (Dimethyltin bis(lauryl mercaptide)), Diethyltin bis(lauryl mercaptide), Dipropyltin bis(
  • the tin catalyst may be used in an amount of 0.0001 parts by weight, 0.0010 parts by weight, 0.0100 parts by weight, or 0.1000 parts by weight based on 100 parts by weight of the polyester containing the repeating unit derived from 1,4-butanediol or a polymer blend containing the same. , may be used in amounts of 10 parts by weight or less, 7 parts by weight or less, 5 parts by weight or less, 3 parts by weight or less, and 1 part by weight or less. If the amount of the tin catalyst added is too small, thermal decomposition of polyester or polymer blend may not occur, and if the amount of the tin catalyst added is too large, the economic feasibility may worsen due to the excessive amount added.
  • the thermal decomposition may be performed at a temperature of 400°C or higher.
  • the thermal decomposition may be carried out at a temperature of 400 °C or higher, for example, 400 °C or higher, 420 °C or higher, 440 °C or higher, 460 °C or higher, 480 °C or higher, 500 °C or higher, 800 °C or lower, 700 °C or lower, 650 °C or higher. It may be °C or lower, 630 °C or lower, 600 °C or lower, or 550 °C or lower. If the thermal decomposition temperature is too low, thermal decomposition of the polyester or polymer blend may not occur, making it difficult to recover butadiene, and if the thermal decomposition temperature is too high, many unexpected impurities may be generated.
  • the thermal decomposition can be carried out solvent free.
  • the polyester containing the 1,4-butanediol-derived repeating unit or the polymer blend containing the same may be thermally decomposed without being dissolved in the solvent.
  • impurities may be formed in the process of thermally decomposing the polyester containing the repeating unit derived from 1,4-butanediol or a polymer blend containing it, and the process of removing the solvent and additional impurities A removal process may be required, which may complicate the process or require additional equipment. Additionally, side reactions may occur during the process of removing the solvent, reducing the recovery rate and purity of monomers. Additionally, there is a disadvantage in that economic efficiency is lowered due to the use of additional solvents.
  • the polyester containing the repeating unit derived from 1,4-butanediol is not particularly limited as long as it is a polymer containing the repeating unit derived from 1,4-butanediol, but contains 1,4-butanol as an aliphatic glycol and dicarboxylic acid. It may be a polyester containing an aliphatic or aromatic dicarboxylic acid as the acid.
  • PBAT polybutylene adipate terephthalate
  • polybutylene adipate isophthalate polybutylene adipate, polybutylene terephthalate, polybutylene isophthalate, polybutylene succinate, polybutylene Na. It may be phthalate, etc.
  • the polyester containing the repeating unit derived from 1,4-butanediol may be the polybutylene adipate terephthalate, and the polybutylene adipate terephthalate is an aliphatic glycol composed of 1,4 butanediol and dicarboxylic acid. It may be an aliphatic/aromatic copolyester manufactured using adipic acid, an aliphatic acid, and dimethyl terephthalate, an aromatic component, as raw materials.
  • the polybutylene adipate terephthalate has a weight average molecular weight (Mw) measured using gel permeation chromatography (GPC) of 50,000 to 300,000 g/mol, more specifically, 50,000 g/mol or more, It has a weight average molecular weight of 70,000 g/mol or more, or 100,000 g/mol or more, and 300,000 g/mol or less, or 200,000 g/mol or less, or 150,000 g/mol or less. If the weight average molecular weight of the polybutylene adipate terephthalate is too small, the overall mechanical properties may be significantly reduced, and if the weight average molecular weight is too large, the processing process may be difficult and processability and elongation may be reduced.
  • Mw weight average molecular weight measured using gel permeation chromatography
  • the polymer blend may be a polymer blend of polylactic acid and polybutylene adipate terephthalate, or a polymer blend of hydroxyalkanoate copolymer and polybutylene adipate terephthalate.
  • the hydroxyalkanoate copolymer may include two or more types of repeating units selected from the group consisting of repeating units derived from 3-hydroxypropionic acid, repeating units derived from lactic acid or lactide, and repeating units derived from glycolic acid or glycolide. .
  • the hydroxyalkanoate copolymer is 3-hydroxypropionate-lactide copolymer, glycolide-lactide copolymer, or 3-hydroxypropionate-glycol. It may be a ride copolymer.
  • the hydroxyalkanoate copolymer is two types selected from the group consisting of a block containing a repeating unit derived from 3-hydroxypropionic acid, a block containing a repeating unit derived from lactic acid or lactide, and a block containing a repeating unit derived from glycolic acid or glycolide. It may be a block copolymer containing the above blocks.
  • the hydroxyalkanoate copolymer may be 3-hydroxypropionate-lactide block copolymer, glycolide-lactide block copolymer, or 3-hydroxyalkanoate copolymer. It may be a propionate-glycolide block copolymer.
  • the method for producing butadiene according to the embodiment is wherein the polyester containing a repeating unit derived from 1,4-butanediol or a polymer blend containing the same includes polylactic acid and a polyester containing a repeating unit derived from 1,4-butanediol. It may be a polymer blend.
  • Preparing lactide by first thermally decomposing a polymer blend containing polylactic acid and polyester containing repeating units derived from 1,4-butanediol;
  • It may include producing butadiene by secondary pyrolysis of the polymer blend containing the first pyrolysis of polylactic acid and polyester containing repeating units derived from 1,4-butanediol.
  • repeating units derived from polylactic acid and 1,4-butanediol may further include melting the polymer blend containing the polyester.
  • Polylactic acid included in the polymer blend may be manufactured by fermentation or polycondensation of lactic acid or lactide.
  • the lactide can be divided into L-lactide composed of L-lactic acid, D-lactide composed of D-lactic acid, and meso-lactide composed of one L-form and one D-form. Additionally, L-lactide and D-lactide mixed in a 50:50 weight ratio may be D,L-lactide or rac-lactide.
  • L- or D-polylactide (PLLA or PDLA) with very high stereoregularity can be obtained. Lactide has a faster crystallization rate and can also have a higher crystallization rate than polylactide, which has low optical purity.
  • the polylactic acid has a weight average molecular weight (Mw) measured using gel permeation chromatography (GPC) of 50,000 to 300,000 g/mol, more specifically, 50,000 g/mol or more, 70,000 g/mol or more. , or 100,000 g/mol or more, and has a weight average molecular weight of 300,000 g/mol or less, or 200,000 g/mol or less, or 150,000 g/mol or less. If the weight average molecular weight of the polylactic acid is too small, the overall mechanical properties may be significantly reduced, and if the weight average molecular weight is too large, the process may be difficult and processability and elongation may be low.
  • Mw weight average molecular weight measured using gel permeation chromatography
  • the lactic acid or lactide may be a plastic and biodegradable compound manufactured from renewable sources through microbial fermentation, and polylactic acid formed by polymerizing it may also contain a large amount of bio raw materials while exhibiting environmental friendliness and biodegradability. there is.
  • lactide produced by thermally decomposing a polymer blend containing polylactic acid containing the bio raw material may also contain a large amount of bio raw material.
  • the polymer blend can be produced by compounding the polylactic acid and polyester containing repeating units derived from 1,4-butanediol in a molten state.
  • the weight ratio of the polylactic acid and the polyester containing repeating units derived from 1,4-butanediol contained in the polymer blend is 1:99 to 99:1, 5:95 to 95:5, 10:90 to 90:10, It may be 15:85 to 85:15, 20:80 to 80:20, 25:75 to 75:25, or 30:70 to 70:30.
  • the first and second thermal decomposition can be performed under solvent-free conditions and under a tin catalyst. Meanwhile, the first thermal decomposition may be carried out at a temperature of 220 °C or higher and 300 °C or lower, for example, 220 °C or higher, 230 °C or higher, 240 °C or higher, 250 °C or higher, 300 °C or lower, 290 °C or lower, 280 °C or higher. It may be below °C. If the first pyrolysis temperature is too low, thermal decomposition of the polymer blend may not be achieved, and if the first pyrolysis temperature is too high, many unexpected impurities may be generated.
  • the first thermal decomposition may be performed at a pressure of more than 0.01 torr and less than 50 torr, for example, more than 0.01 torr, more than 0.05 torr, more than 0.1 torr, more than 0.5 torr, more than 1 torr, more than 2 torr, more than 4 torr. , may be 5 torr or more, 50 torr or less, 40 torr or less, 30 torr or less, and 20 torr or less, but is not limited thereto. The lower the pyrolysis pressure, the easier it may be to separate and recover lactide.
  • the lactide After the step of producing lactide by first thermal decomposition of the polymer blend, the lactide can be separated by reduced pressure distillation.
  • the first thermal decomposition is performed under reduced pressure conditions at a pressure exceeding 1 torr, and the lactide produced at this time can be recovered through reduced pressure distillation. Additionally, even if the first pyrolysis is not performed under reduced pressure conditions, the lactide can be recovered through distillation.
  • Butadiene can be produced by secondary pyrolysis of the polymer blend remaining after the lactide is recovered.
  • the secondary thermal decomposition may be performed at a temperature of 400 °C or higher, for example, 400 °C or higher, 420 °C or higher, 440 °C or higher, 460 °C or higher, 480 °C or higher, 500 °C or higher, 800 °C or lower, 700 °C or lower. , may be 650°C or lower, 630°C or lower, 600°C or lower, and 550°C or lower. If the secondary pyrolysis temperature is too low, secondary pyrolysis of the polymer blend may not occur, making it difficult to recover butadiene, and if the secondary pyrolysis temperature is too high, many unexpected impurities may be generated.
  • the difference between the first pyrolysis temperature and the second pyrolysis temperature may be 150 °C or more and 350 °C or less, for example, 150 °C or more, 160 °C or more, 170 °C or more, 180 °C or more, 190 °C or more, 200 °C or more, It may be 210°C or higher, 350°C or lower, 340°C or lower, 330°C or lower, 320°C or lower, and 310°C or lower. If the difference between the first and second pyrolysis temperatures is too small, recovery of the butadiene may be difficult, and if the difference between the first and second pyrolysis temperatures is too large, many unexpected impurities may be generated. . Butadiene produced through the secondary pyrolysis can be recovered using a gas collection device.
  • the step of producing butadiene by pyrolyzing polyester containing a repeating unit derived from 1,4-butanediol or a polymer blend containing the same the step of producing butadiene by pyrolyzing polyester containing a repeating unit derived from 1,4-butanediol or a polymer blend containing the same,
  • Preparing lactide by first thermal decomposing a polymer blend containing the 3-hydroxypropionate-lactide copolymer and a polyester containing a repeating unit derived from 1,4-butanediol;
  • It may include the step of producing butadiene by tertiary pyrolysis of the polymer blend containing the secondary pyrolysis of the 3-hydroxypropionate-lactide copolymer and polyester containing a repeating unit derived from 1,4-butanediol. there is.
  • step 3 -It may further include melting a polymer blend containing a hydroxypropionate-lactide copolymer and a polyester containing a repeating unit derived from 1,4-butanediol.
  • the 3-hydroxypropionate-lactide copolymer may be a block copolymer obtained by polymerizing polylactic acid prepolymer and poly(3-hydroxypropionate) prepolymer.
  • the 3-hydroxypropionate-lactide copolymer exhibits the excellent tensile strength and elastic modulus characteristics of the polylactic acid prepolymer, while the poly(3-hydroxypropionate) prepolymer has a glass transition temperature (Tg).
  • Tg glass transition temperature
  • the polylactic acid prepolymer may be manufactured by fermentation or polycondensation of lactic acid.
  • the polylactic acid prepolymer may have a weight average molecular weight of 1,000 g/mol or more, or 5,000 g/mol or more, or 6,000 g/mol or more, or 8,000 g/mol or more, and 50,000 g/mol or less, or 30,000 g/mol or less,
  • the polylactic acid prepolymer must be greater than 20,000 g/mol, or 22,000 g/mol or more, or 23,000 g/mol.
  • the weight average molecular weight of the polylactic acid prepolymer is less than 20,000 g/mol, the polymer crystals are small and it is difficult to maintain the crystallinity of the polymer in the final manufactured block copolymer. If the weight average molecular weight of the polylactic acid prepolymer exceeds 50,000 g/mol, it is difficult to maintain the crystallinity of the polymer. During polymerization, the side reaction rate occurring within the prepolymer chain becomes faster than the reaction rate between polylactic acid prepolymers. Meanwhile, 'lactic acid' used in the present invention refers to L-lactic acid, D-lactic acid, or a mixture thereof.
  • the poly(3-hydroxypropionate) prepolymer may be manufactured by fermenting or condensation polymerization of 3-hydroxypropionate.
  • the weight average molecular weight of the poly(3-hydroxypropionate) prepolymer is 1,000 g/mol or more, or 5,000 g/mol or more, or 8,000 g/mol or more, or 8,500 g/mol or more, and 50,000 g/mol or less, Alternatively, it may be 30,000 g/mol or less, and when it is desired to increase the crystallinity of the repeating unit derived from the poly(3-hydroxypropionate) prepolymer in the final manufactured block copolymer, the poly(3-hydroxypropionate)
  • the prepolymer has a high weight average molecular weight of more than 20,000 g/mol, or more than 22,000 g/mol, or more than 25,000 g/mol, and less than or equal to 50,000 g/mol, or less than or equal to 30,000 g/mol, or less than or equal to 2
  • the weight average molecular weight of the poly(3-hydroxypropionate) prepolymer is 20,000 g/mol or less, the polymer crystals are small, making it difficult to maintain the crystallinity of the polymer in the final manufactured block copolymer. It is difficult, and if the weight average molecular weight of the poly(3-hydroxypropionate) prepolymer exceeds 50,000 g/mol, the side reaction rate occurring inside the prepolymer chain is higher than the reaction rate between poly(3-hydroxypropionate) prepolymers during polymerization. becomes faster.
  • At least one of the polylactic acid prepolymer and the poly(3-hydroxypropionate) prepolymer may have a weight average molecular weight of more than 20,000 g/mol and less than or equal to 50,000 g/mol.
  • the 3-hydroxypropionate-lactide copolymer is a block copolymer in which polylactic acid prepolymer and poly(3-hydroxypropionate) prepolymer are polymerized, and in the block copolymer, the polylactic acid prepolymer and poly(3 -Hydroxypropionate)
  • the weight ratio of the prepolymer is 95:5 to 50:50, 90:10 to 55:45, 90:10 to 60:40, 90:10 to 70:30, or 90:10 to 80:20. It can be.
  • the poly(3-hydroxypropionate) prepolymer may increase brittleness, and the poly(3-hydroxypropionate) prepolymer may increase brittleness. If too much prepolymer is included, the molecular weight may be lowered and processability and heat stability may be reduced.
  • the 3-hydroxypropionate-lactide copolymer has a weight average molecular weight (Mw) measured using gel permeation chromatography (GPC) of 50,000 to 300,000 g/mol, more specifically 50,000. g/mol or more, 70,000 g/mol or more, or 100,000 g/mol or more, and has a weight average molecular weight of 300,000 g/mol or less, or 200,000 g/mol or less, or 150,000 g/mol or less. If the weight average molecular weight of the hydroxyalkanoate-lactide copolymer is too small, the overall mechanical properties may be significantly reduced, and if the weight average molecular weight is too large, the process may be difficult and processability and elongation may be low.
  • Mw weight average molecular weight measured using gel permeation chromatography
  • the lactic acid and 3-hydroxypropionate may be plastic and biodegradable compounds produced from renewable sources by microbial fermentation, and polylactic acid prepolymer and poly(3-hydroxypropionate) formed by polymerizing them
  • the block copolymer containing a prepolymer may also contain a large amount of bio raw materials while exhibiting environmental friendliness and biodegradability.
  • lactide and acrylic acid produced by thermally decomposing a copolymer containing the bio raw materials may also contain a large amount of bio raw materials.
  • the polymer blend can be prepared by compounding the 3-hydroxypropionate-lactide copolymer with a polyester containing a repeating unit derived from 1,4-butanediol in a molten state.
  • the weight ratio of the 3-hydroxypropionate-lactide copolymer and the polyester containing repeating units derived from 1,4-butanediol contained in the polymer blend is 1:99 to 99:1, 5:95 to 95: 5, 10:90 to 90:10, 15:85 to 85:15, 20:80 to 80:20, 25:75 to 75:25, or 30:70 to 70:30.
  • the first, second and third thermal decomposition may be carried out under solvent-free conditions and under a tin catalyst. Meanwhile, the first thermal decomposition may be performed at a temperature of 200 °C or higher and 250 °C or lower, for example, 200 °C or higher, 210 °C or higher, 220 °C or higher, 250 °C or lower, 240 °C or lower, 230 °C or lower. . If the first pyrolysis temperature is too low, thermal decomposition of the polymer blend may not be achieved, and if the first pyrolysis temperature is too high, many unexpected impurities may be generated.
  • the first thermal decomposition may be performed at a pressure of more than 0.01 torr and less than 50 torr, for example, more than 0.01 torr, more than 0.05 torr, more than 0.1 torr, more than 0.5 torr, more than 1 torr, more than 2 torr, more than 4 torr. , may be 5 torr or more, 50 torr or less, 40 torr or less, 30 torr or less, and 20 torr or less, but is not limited thereto. The lower the pyrolysis pressure, the easier it may be to separate and recover lactide.
  • the lactide can be separated by reduced pressure distillation.
  • the first thermal decomposition is performed under reduced pressure conditions at a pressure exceeding 1 torr, and the lactide produced at this time can be recovered through reduced pressure distillation. Additionally, even if the first pyrolysis is not performed under reduced pressure conditions, the lactide can be recovered through distillation.
  • Acrylic acid can be produced by secondary pyrolysis of the polymer blend remaining after the lactide is recovered.
  • the secondary thermal decomposition may be carried out at a temperature of 260 °C or higher and 350 °C or lower, for example, 260 °C or higher, 270 °C or higher, 280 °C or higher, 290 °C or higher, 350 °C or lower, 340 °C or lower, 330 °C or higher. It may be below °C. If the secondary pyrolysis temperature is too low, secondary pyrolysis of the polymer blend may not occur and acrylic acid may not be produced, and if the secondary pyrolysis temperature is too high, many unexpected impurities may be generated.
  • Butadiene can be produced by third thermal decomposition of the polymer blend remaining after the acrylic acid is recovered.
  • the third thermal decomposition may be performed at a temperature of 400 °C or higher, for example, 400 °C or higher, 420 °C or higher, 440 °C or higher, 460 °C or higher, 480 °C or higher, 500 °C or higher, 800 °C or lower, 700 °C or lower. , may be 650°C or lower, 630°C or lower, 600°C or lower, and 550°C or lower. If the tertiary pyrolysis temperature is too low, tertiary pyrolysis of the polymer blend may not occur, making it difficult to recover butadiene, and if the tertiary pyrolysis temperature is too high, many unexpected impurities may be generated.
  • the acrylic acid After producing acrylic acid by performing secondary pyrolysis of the first pyrolyzed polymer blend, the acrylic acid can be separated by reduced pressure distillation.
  • the secondary thermal decomposition is performed under reduced pressure conditions at a pressure exceeding 1 torr, and the acrylic acid produced at this time can be recovered through reduced pressure distillation. Additionally, even if the secondary thermal decomposition is not performed under reduced pressure conditions, the acrylic acid can be recovered through distillation.
  • the difference between the first pyrolysis temperature and the second pyrolysis temperature may be 20 °C or more and 100 °C or less, for example, 20 °C or more, 30 °C or more, 40 °C or more, 50 °C or more, 100 °C or less, It may be 90°C or lower, 80°C or lower, or 70°C or lower. If the difference between the first and second pyrolysis temperatures is too small, recovery of the acrylic acid may be difficult, and if the difference between the first and second pyrolysis temperatures is too large, many unexpected impurities may be generated. .
  • Butadiene can be produced by third thermal decomposition of the polymer blend remaining after the acrylic acid is recovered.
  • the third thermal decomposition may be performed at a temperature of 400 °C or higher, for example, 400 °C or higher, 420 °C or higher, 440 °C or higher, 460 °C or higher, 480 °C or higher, 500 °C or higher, 800 °C or lower, 700 °C or lower. , may be 650°C or lower, 630°C or lower, 600°C or lower, and 550°C or lower. If the tertiary pyrolysis temperature is too low, tertiary pyrolysis of the polymer blend may not occur, making it difficult to recover butadiene, and if the tertiary pyrolysis temperature is too high, many unexpected impurities may be generated.
  • the difference between the secondary pyrolysis temperature and the tertiary pyrolysis temperature may be 150 °C or more and 350 °C or less, for example, 150 °C or more, 160 °C or more, 170 °C or more, 180 °C or more, 190 °C or more, 200 °C or more, It may be 210°C or higher, 350°C or lower, 340°C or lower, 330°C or lower, 320°C or lower, and 310°C or lower.
  • Butadiene produced through the third pyrolysis can be recovered using a gas collection device.
  • the polyester containing a repeating unit derived from 1,4-butanediol or a polymer blend containing the same is a glycolide-lactide copolymer and a repeating unit derived from 1,4-butanediol. It may be polyester.
  • Preparing lactide and glycolide by first thermal decomposing a polymer blend containing the glycolide-lactide copolymer and a polyester containing a repeating unit derived from 1,4-butanediol; and
  • It may include the step of producing butadiene by secondary pyrolysis of the polymer blend containing the primary pyrolysis of the glycolide-lactide copolymer and polyester containing a repeating unit derived from 1,4-butanediol.
  • the glycolide- It may further include melting the polymer blend including a lactide copolymer and a polyester containing repeating units derived from 1,4-butanediol.
  • glycolide-lactide copolymer included in the polymer blend is not particularly limited as long as it is a copolymer of glycolide monomer and lactide monomer, but for example, it may be a random copolymer of glycolide monomer and lactide monomer. there is.
  • the glycolide-lactide copolymer may be a block copolymer including one or more polyglycolide blocks and one or more polylactide blocks. That is, the glycolide-lactide copolymer may be a block copolymer obtained by polymerizing polylactide prepolymer and polyglycolide prepolymer. As the glycolide-lactide copolymer contains the above-mentioned blocks, it can exhibit the environmental friendliness and biodegradability of polyglycolide and polylactide.
  • the polylactide prepolymer may be manufactured by fermentation or polycondensation of lactic acid.
  • the polylactide prepolymer may have a weight average molecular weight of 1,000 g/mol or more, or 5,000 g/mol or more, or 6,000 g/mol or more, or 8,000 g/mol or more, and 50,000 g/mol or less, or 30,000 g/mol or less.
  • the polylactide prepolymer is greater than 20,000 g/mol, or more than 22,000 g/mol, or 23,000 g/mol.
  • the weight average molecular weight of the polylactide prepolymer is 20,000 g/mol or less, the polymer crystals are small and it is difficult to maintain the crystallinity of the polymer in the final manufactured block copolymer, and the weight average molecular weight of the polylactide prepolymer is 50,000 g/mol. If it is exceeded, the rate of side reactions occurring inside the prepolymer chain becomes faster than the rate of reaction between polylactide prepolymers during polymerization.
  • 'lactic acid' used in the present invention refers to L-lactic acid, D-lactic acid, or a mixture thereof.
  • the polyglycolide prepolymer may be manufactured by fermenting or condensation polymerization of glycolide.
  • the weight average molecular weight of the polyglycolide prepolymer may be 1,000 g/mol or more, or 5,000 g/mol or more, or 8,000 g/mol or more, or 8,500 g/mol or more, and 50,000 g/mol or less, or 30,000 g/mol or less.
  • the polyglycolide prepolymer must be greater than 20,000 g/mol, or greater than 22,000 g/mol, or greater than 25,000 g/mol. and preferably has a high weight average molecular weight of 50,000 g/mol or less, or 30,000 g/mol or less, or 28,000 g/mol or less.
  • the weight average molecular weight of the polyglycolide prepolymer is 20,000 g/mol or less, the crystals of the polymer are small, making it difficult to maintain the crystallinity of the polymer in the final manufactured block copolymer. If the weight average molecular weight exceeds 50,000 g/mol, the side reaction rate that occurs inside the prepolymer chain becomes faster than the reaction rate between polyglycolide prepolymers during polymerization.
  • At least one of the polylactide prepolymer and the polyglycolide prepolymer may have a weight average molecular weight of more than 20,000 g/mol and less than 50,000 g/mol.
  • the glycolide-lactide copolymer is a block copolymer in which polylactide prepolymer and polyglycolide prepolymer are polymerized, and the weight ratio of the polylactide prepolymer and polyglycolide prepolymer in the block copolymer is 90:10 to 30: It may be 70, 80:20 to 40:60, or 75:25 to 50:50. If too little of the polyglycolide prepolymer is included in the polylactide prepolymer, brittleness may increase, and if too much of the polyglycolide prepolymer is included in the polylactide prepolymer, the molecular weight is lowered, thereby improving processability and heat resistance. Stability may be reduced.
  • the glycolide-lactide copolymer has a weight average molecular weight (Mw) measured using gel permeation chromatography (GPC) of 20,000 to 300,000 g/mol, more specifically, 20,000 g/mol or more, 30,000 g/mol or more, 40,000 g/mol or more, 50,000 g/mol or more, 70,000 g/mol or more, or 100,000 g/mol or more, and 300,000 g/mol or less, or 200,000 g/mol or less, or 150,000 g/mol or less It has a weight average molecular weight of .
  • Mw weight average molecular weight measured using gel permeation chromatography
  • the weight average molecular weight of the glycolide-lactide copolymer is too small, the overall mechanical properties may be significantly reduced, and if the weight average molecular weight is too large, the process may be difficult and processability and elongation may be low.
  • the polymer blend can be produced by compounding the glycolide-lactide copolymer and polyester containing repeating units derived from 1,4-butanediol in a molten state.
  • the weight ratio of the glycolide-lactide copolymer and the polyester containing repeating units derived from 1,4-butanediol contained in the polymer blend is 1:99 to 99:1, 5:95 to 95:5, and 10:90. to 90:10, 15:85 to 85:15, 20:80 to 80:20, 25:75 to 75:25, or 30:70 to 70:30.
  • the first and second thermal decomposition may be performed without a solvent or under a tin catalyst. Meanwhile, the first thermal decomposition may be performed at a temperature of 200 °C or higher and 380 °C or lower, for example, 200 °C or higher, 210 °C or higher, 220 °C or higher, 380 °C or lower, 300 °C or lower, or 250 °C or lower. . If the first pyrolysis temperature is too low, thermal decomposition of the polymer blend may not occur, and if the first pyrolysis temperature is too high, many unexpected impurities may be generated.
  • the first thermal decomposition may be performed at a pressure of more than 0.01 torr and less than 50 torr, for example, more than 0.01 torr, more than 0.05 torr, more than 0.1 torr, more than 0.5 torr, more than 1 torr, more than 2 torr, more than 4 torr. , may be 5 torr or more, 50 torr or less, 40 torr or less, 30 torr or less, and 20 torr or less, but is not limited thereto. The lower the pyrolysis pressure, the easier it may be to separate and recover lactide.
  • the lactide and glycolide After the step of producing lactide and glycolide by first thermal decomposition of the polymer blend, the lactide and glycolide can be separated by reduced pressure distillation.
  • the first thermal decomposition is performed under reduced pressure conditions at a pressure exceeding 1 torr, and the lactide and glycolide produced at this time can be recovered through reduced pressure distillation. Additionally, even if the first pyrolysis is not performed under reduced pressure conditions, the lactide and glycolide can be recovered through distillation.
  • Butadiene can be produced by secondary pyrolysis of the polymer blend remaining after the lactide and glycolide are recovered.
  • the secondary thermal decomposition may be performed at a temperature of 400 °C or higher, for example, 400 °C or higher, 420 °C or higher, 440 °C or higher, 460 °C or higher, 480 °C or higher, 500 °C or higher, 800 °C or lower, 700 °C or lower. , may be 650°C or lower, 630°C or lower, 600°C or lower, and 550°C or lower. If the secondary pyrolysis temperature is too low, secondary pyrolysis of the polymer blend may not occur, making it difficult to recover butadiene, and if the secondary pyrolysis temperature is too high, many unexpected impurities may be generated.
  • the difference between the first pyrolysis temperature and the second pyrolysis temperature may be 100 °C or more and 400 °C or less, 100 °C or more, 150 °C or more, 180 °C or more, 200 °C or more, 220 °C or more, 250 °C or more, 280 °C or more. It may be °C or higher, and may be 400 °C or lower, 380 °C or lower, 350 °C or lower, 330 °C or lower, and 300 °C or lower.
  • Butadiene produced through the secondary pyrolysis can be recovered using a gas collection device.
  • the polyester containing a repeating unit derived from 1,4-butanediol or a polymer blend containing the same is derived from 3-hydroxypropionate-glycolide copolymer and 1,4-butanediol. It may be a polymer blend containing polyester containing repeating units.
  • Preparing glycolide by first thermal decomposing a polymer blend containing the 3-hydroxypropionate-glycolide copolymer and a polyester containing a repeating unit derived from 1,4-butanediol;
  • It may include the step of producing butadiene by tertiary pyrolysis of the polymer blend containing the secondary pyrolysis of the 3-hydroxypropionate-glycolide copolymer and polyester containing a repeating unit derived from 1,4-butanediol. there is.
  • step 3 -It may further include melting a polymer blend containing a hydroxypropionate-glycolide copolymer and a polyester containing a repeating unit derived from 1,4-butanediol.
  • the 3-hydroxypropionate-glycolide copolymer includes a block containing a repeating unit derived from 3-hydroxypropionate and a block containing a repeating unit derived from glycolide, and these blocks are directly bonded or ester bonded. , amide bond, urethane bond, or carbonate bond, it can compensate for the disadvantage of low elongation characteristics of biodegradable resins containing only polyglycolide. Additionally, these copolymers can have excellent biodegradability while complementing the mechanical properties of each homopolymer.
  • the 3-hydroxypropionate-glycolide copolymer includes a block containing a 3-hydroxypropionate-derived repeating unit represented by the following formula (2), and a glycolide-derived repeating unit represented by the following formula (3) It can contain blocks that contain it.
  • the repeating unit derived from 3-hydroxypropionate represented by Formula 2 has the advantage of excellent mechanical properties and a high elongation to break due to a glass transition temperature (Tg) as low as -20°C. Therefore, by chemically combining poly(3-hydroxypropionate) and polyglycolide to produce a block copolymer, a biodegradable material with excellent mechanical properties can be produced.
  • Tg glass transition temperature
  • repeating unit represented by Formula 2 and the repeating unit represented by Formula 3 may be linked by a direct bond, an ester bond, an amide bond, a urethane bond, a urea bond, or a carbonate bond, for example, the 3-hydroxypro
  • the cypionate-glycolide copolymer may be a block copolymer represented by the following formula (1).
  • R 1 and R 2 are each independently hydrogen, N, O, S, or substituted or unsubstituted C 1-20 alkyl,
  • R' is each independently hydrogen, or C 1-20 alkyl
  • L is a direct bond; Substituted or unsubstituted C 1-10 alkylene; Substituted or unsubstituted C 6-60 arylene; or a C 2-60 heteroarylene containing one or more heteroatoms selected from the group consisting of substituted or unsubstituted N, O, and S,
  • n and m may each independently be an integer from 1 to 10,000.
  • n refers to the number of repetitions of the repeating unit derived from 3-hydroxypropionate, and when introduced within the above range, physical properties such as elongation can be adjusted while maintaining the inherent physical properties of polyglycolide.
  • m refers to the number of repeats of the glycolide-derived repeating unit.
  • X 1 , X 2 , and L may be a direct bond.
  • the above Chemical Formula 1 may be expressed as the following Chemical Formula 1-1.
  • n and m may be as described above.
  • n is 10 to 700
  • m can be 10 to 700
  • n is 20 or more, 30 or more, 40 or more, 50 or more, or 60 or more, and is 650 or less, 600 or less, 550 or less, 500 or less.
  • m may be 20 or more, 30 or more, 40 or more, 50 or more, or 60 or more, and may be 650 or less, 600 or less, 550 or less, 500 or less, or 450 or less.
  • the 3-hydroxypropionate-glycolide copolymer may have a weight average molecular weight of 10,000 g/mol or more and 500,000 g/mol or less.
  • the weight average molecular weight of the copolymer is 12,000 g/mol or more, 15,000 g/mol or more, 20,000 g/mol or more, 25,000 g/mol or more, or 30,000 g/mol or more, and 480,000 g/mol or less, It may be less than or equal to 460,000 g/mol, less than or equal to 440,000 g/mol, or less than or equal to 420,000 g/mol.
  • the 3-hydroxypropionate-glycolide copolymer may be a block copolymer obtained by ring-opening polymerization of a glycolide monomer in the presence of a poly(3-hydroxypropionate) initiator.
  • the 3-hydroxypropionate-glycolide copolymer may be prepared by preparing poly(3-hydroxypropionate) (step 1); and preparing a block copolymer by ring-opening polymerizing a glycolide monomer in the presence of the poly(3-hydroxypropionate) initiator (step 2).
  • Step 1 is a step of preparing the poly(3-hydroxypropionate), wherein the poly(3-hydroxypropionate) refers to a homopolymer of 3-hydroxypropionic acid, and the n and Those manufactured by adjusting the degree of polymerization taking into account the range of m can be used.
  • the poly(3-hydroxypropionate) initiator has a weight average molecular weight of 1,000 g/mol or more and 500,000 g/mol or less, 2,000 g/mol or more and 400,000 g/mol or less, 3,000 g/mol or more and 300,000 g/mol or less, It may be 4,000 g/mol or more and 200,000 g/mol or less, 5,000 g/mol or more and 100,000 g/mol or less, and 10,000 g/mol or more and 90,000 g/mol or less.
  • Step 2 may be a step of ring-opening polymerization of glycolide monomer using poly(3-hydroxypropionate) as an initiator.
  • Step 2 can be carried out as bulk polymerization substantially without using a solvent.
  • substantially not using a solvent may include the use of a small amount of solvent to dissolve the catalyst, for example, a maximum of less than 1 ml of solvent per kg of monomer used.
  • the weight ratio of the poly(3-hydroxypropionate) initiator and glycolide monomer is 1:99 to 99:1, 5:95 to 90:10, 10:90 to 80:20, and 15:85 to 70:30. , or 20:80 to 50:50.
  • the glycolide ring-opening polymerization reaction since it is accompanied, it may be carried out in the presence of a glycolide ring-opening catalyst.
  • the ring-opening catalyst may be a catalyst represented by the following formula (4).
  • M is Al, Mg, Zn, Ca, Sn, Fe, Y, Sm, Lu, Ti or Zr,
  • p is an integer from 0 to 2
  • a 1 and A 2 may each independently be an alkoxy or carboxyl group.
  • the catalyst represented by Chemical Formula 4 may be tin(II) 2-ethylhexanoate (Sn(Oct) 2 ).
  • Preparation of the 3-hydroxypropionate-glycolide copolymer may be performed at a temperature of 150 to 200° C. for 5 minutes to 10 hours or for 10 minutes to 1 hour.
  • the polymer blend can be prepared by compounding the 3-hydroxypropionate-glycolide copolymer and polyester containing repeating units derived from 1,4-butanediol in a molten state.
  • the weight ratio of the 3-hydroxypropionate-glycolide copolymer and the polyester containing repeating units derived from 1,4-butanediol contained in the polymer blend is 1:99 to 99:1, 5:95 to 95: 5, 10:90 to 90:10, 15:85 to 85:15, 20:80 to 80:20, 25:75 to 75:25, or 30:70 to 70:30.
  • the first, second and third thermal decomposition may be performed without a solvent or under a tin catalyst.
  • the first thermal decomposition may be carried out at a temperature of 200 °C or higher and 250 °C or lower, for example, 200 °C or higher, 210 °C or higher, 220 °C or higher, 250 °C or lower, 240 °C or lower, 230 °C or lower. If the first pyrolysis temperature is too low, thermal decomposition of the polymer blend may not be achieved, and if the first pyrolysis temperature is too high, many unexpected impurities may be generated.
  • the first thermal decomposition may be performed at a pressure of more than 0.01 torr and less than 50 torr, for example, more than 0.01 torr, more than 0.05 torr, more than 0.1 torr, more than 0.5 torr, more than 1 torr, more than 2 torr, more than 4 torr. , may be 5 torr or more, 50 torr or less, 40 torr or less, 30 torr or less, and 20 torr or less, but is not limited thereto. The lower the pyrolysis pressure, the easier the separation and recovery of glycolide.
  • the glycolide After the step of producing glycolide by first thermal decomposition of the polymer blend, the glycolide can be separated by reduced pressure distillation.
  • the first thermal decomposition is performed under reduced pressure conditions at a pressure exceeding 1 torr, and the glycolide produced at this time can be recovered through reduced pressure distillation. Additionally, even if the first thermal decomposition is not performed under reduced pressure conditions, the glycolide can be recovered through distillation.
  • Acrylic acid can be produced by secondary pyrolysis of the polymer blend remaining after the glycolide is recovered.
  • the secondary thermal decomposition may be carried out at a temperature of 260 °C or higher and 380 °C or lower, for example, 260 °C or higher, 270 °C or higher, 280 °C or higher, 290 °C or higher, 380 °C or lower, 350 °C or lower, 330 °C or higher. It may be below °C. If the secondary pyrolysis temperature is too low, secondary pyrolysis of the polymer blend may not occur and acrylic acid may not be produced, and if the secondary pyrolysis temperature is too high, many unexpected impurities may be generated.
  • Butadiene can be produced by third thermal decomposition of the polymer blend remaining after the acrylic acid is recovered.
  • the third thermal decomposition may be performed at a temperature of 400 °C or higher, for example, 400 °C or higher, 420 °C or higher, 440 °C or higher, 460 °C or higher, 480 °C or higher, 500 °C or higher, 800 °C or lower, 700 °C or lower. , may be 650°C or lower, 630°C or lower, 600°C or lower, and 550°C or lower. If the tertiary pyrolysis temperature is too low, tertiary pyrolysis of the polymer blend may not occur, making it difficult to recover butadiene, and if the tertiary pyrolysis temperature is too high, many unexpected impurities may be generated.
  • the acrylic acid After producing acrylic acid by performing secondary pyrolysis of the first pyrolyzed polymer blend, the acrylic acid can be separated by reduced pressure distillation.
  • the secondary thermal decomposition is performed under reduced pressure conditions at a pressure exceeding 1 torr, and the acrylic acid produced at this time can be recovered through reduced pressure distillation. Additionally, even if the secondary thermal decomposition is not performed under reduced pressure conditions, the acrylic acid can be recovered through distillation.
  • the difference between the first pyrolysis temperature and the second pyrolysis temperature may be 20 °C or more and 100 °C or less, for example, 20 °C or more, 30 °C or more, 40 °C or more, 50 °C or more, 100 °C or less, It may be 90°C or lower, 80°C or lower, or 70°C or lower. If the difference between the first and second pyrolysis temperatures is too small, recovery of the acrylic acid may be difficult, and if the difference between the first and second pyrolysis temperatures is too large, many unexpected impurities may be generated. .
  • the difference between the secondary pyrolysis temperature and the tertiary pyrolysis temperature may be 150 °C or more and 350 °C or less, for example, 150 °C or more, 160 °C or more, 170 °C or more, 180 °C or more, 190 °C or more, 200 °C or more, It may be 210°C or higher, 350°C or lower, 340°C or lower, 330°C or lower, 320°C or lower, and 310°C or lower.
  • Butadiene produced through the third pyrolysis can be recovered using a gas collection device.
  • the polyester containing a repeating unit derived from 1,4-butanediol or a polymer blend containing the same may be a polyester containing a repeating unit derived from 1,4-butanediol.
  • It may include the step of producing butadiene by secondary pyrolysis of the polyester containing repeating units derived from 1,4-butanediol that has been subjected to primary pyrolysis.
  • the step of producing 1,4-butanediol by first pyrolyzing the polyester containing the repeating unit derived from 1,4-butanediol the step of melting the polyester containing the repeating unit derived from 1,4-butanediol. More may be included.
  • the first and second thermal decomposition can be performed under solvent-free conditions and under a tin catalyst.
  • the first thermal decomposition may be carried out at a temperature of 220 °C or higher and 350 °C or lower, for example, 220 °C or higher, 230 °C or higher, 240 °C or higher, 250 °C or higher, 350 °C or lower, 340 °C or lower, 330 °C or lower. , may be 320°C or lower, 310°C or lower, and 300°C or lower.
  • the pyrolysis of the polyester containing the 1,4-butanediol-derived repeating unit may not be achieved, and if the first pyrolysis temperature is too high, many unexpected impurities may be generated. .
  • the first thermal decomposition may be performed at a pressure of more than 0.01 torr and less than 50 torr, for example, more than 0.01 torr, more than 0.05 torr, more than 0.1 torr, more than 0.5 torr, more than 1 torr, more than 2 torr, more than 4 torr. , may be 5 torr or more, 50 torr or less, 40 torr or less, 30 torr or less, and 20 torr or less, but is not limited thereto.
  • the lower the pyrolysis pressure the easier it may be to separate and recover 1,4-butanediol.
  • the 1,4-butanediol After the step of producing 1,4-butanediol by first thermal decomposition of the polyester containing the repeating unit derived from 1,4-butanediol, the 1,4-butanediol can be separated by distillation or reduced pressure distillation.
  • the first thermal decomposition is performed under reduced pressure conditions at a pressure exceeding 1 torr, and the 1,4-butanediol produced at this time can be recovered through reduced pressure distillation. Additionally, even if the first thermal decomposition is not performed under reduced pressure conditions, the 1,4-butanediol can be recovered through distillation.
  • Butadiene can be produced by secondary thermal decomposition of the polyester containing the 1,4-butanediol-derived repeating unit remaining after the 1,4-butanediol is recovered.
  • the secondary thermal decomposition may be carried out at a temperature of 400 °C or higher, for example, 400 °C or higher, 420 °C or higher, 440 °C or higher, 460 °C or higher, 480 °C or higher, 500 °C or higher, 800 °C or lower, 700 °C or higher. It may be °C or lower, 650 °C or lower, 630 °C or lower, 600 °C or lower, or 550 °C or lower.
  • the thermal decomposition of the polyester containing the repeating unit derived from 1,4-butanediol in the first pyrolysis may not occur, making it difficult to recover butadiene, and if the secondary pyrolysis temperature is too high, it may be difficult to recover butadiene. A lot of impurities may be created that were not made.
  • the difference between the first pyrolysis temperature and the second pyrolysis temperature may be 100 °C or more and 300 °C or less, for example, 100 °C or more, 120 °C or more, 140 °C or more, 160 °C or more, 180 °C or more, 200 °C or more. and may be 300°C or lower, 280°C or lower, 270°C or lower, 260°C or lower, and 250°C or lower. If the difference between the first and second pyrolysis temperatures is too small, recovery of the butadiene may be difficult, and if the difference between the first and second pyrolysis temperatures is too large, many unexpected impurities may be generated. . Butadiene produced through the secondary pyrolysis can be recovered using a gas collection device.
  • the recovery rate of lactide, glycolide, acrylic acid, 1,4-butanediol and/or butadiene is 30% or more, 50% or more, 60% or more, 70% or more, 80% or more, or 90% or more, for example, 40 to 99.9%, 50 to 99.9%, 60 to 99.9%, 70 to 99.9%, 80 to 99.9%, 90 to 99.9%, 40 to 99%, 50 to 99%, 60 to 99%, 70 to 99%, 80 to 99%, 90 to 99%, 40 to 97%, 50 to 97%, 60 to 97%, 70 to 97%, 80 to 97%, 90 to 97%, 40 to 95%, 50 to 95%, It may be 60 to 95%, 70 to 95%, 80 to 95%, or 90 to 95%.
  • the recovery rate may be calculated on a mole basis.
  • each of the lactide, glycolide, acrylic acid, 1,4-butanediol and/or butadiene is 50% or more, 60% or more, 70% or more, 80% or more, or 90% or more, such as 40 to 99.9%, 50 to 99.9%, 60 to 99.9%, 70 to 99.9%, 80 to 99.9%, 90 to 99.9%, 40 to 99%, 50 to 99%, 60 to 99%, 70 to 99%, 80 to 99%, 90 to 99%, 40 to 97%, 50 to 97%, 60 to 97%, 70 to 97%, 80 to 97%, 90 to 97%, 40 to 95%, 50 to 95%, 60 to 95%, It may be 70 to 95%, 80 to 95%, or 90 to 95%.
  • a butadiene production method that converts polyester containing repeating units derived from 1,4-butanediol or a polymer blend containing it into recyclable butadiene, etc. with high purity and high yield in an environmentally friendly and economical manner. It can be.
  • the polylactic acid prepolymer and the poly(3-hydroxypropionate) prepolymer were mixed in a 100 ml Schlenk flask in an oil bath at a weight ratio of 8:2, added to a total content of 30 g, and p-toluenesulfonic acid ( 90 mg of p-TSA) was added, and annealing was performed at 60°C for 3 hours.
  • p-TSA p-toluenesulfonic acid
  • 3-hydroxypropionate-lactide block copolymer was prepared by solid-phase polymerization reaction using an evaporator and mixing at 150°C and 0.5 mbar for 24 hours.
  • the weight average molecular weight of the polylactic acid prepolymer, poly(3-hydroxypropionate) prepolymer, and block copolymer was measured using gel permeation chromatography (GPC).
  • PBAT polybutylene adipate terephthalate
  • PSH hydroxyalkanoate-glycolide copolymer
  • Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Comparative Example 1 Comparative example 2 episode transference number (%) Lactide 83.3 75.7 87.5 87.5 83 81 - 87.0 - glycolide - - - - 81 - - acrylic acid - - 57.1 66.7 - - 59 - 70.0 butadiene 68.1 46.4 52.8 53.3 62 58 63 - - Purity (%) Lactide ⁇ 98.0 ⁇ 98.0 ⁇ 98.0 > 98 > 98 - ⁇ 98.0 - glycolide - - - > 98 > 98 ⁇ 98 - - acrylic acid - - ⁇ 98.0 ⁇ 98.0 - - 99 - 99.4 butadiene ⁇ 99.0 ⁇ 99.0 ⁇ 98.0 ⁇ 98.0 > 98 > 98 > 98 ⁇ 99 - - -
  • Example 8 Example 9 1,4-Butanediol and butadiene recovery (g) (1,4-butanediol:butadiene weight ratio) 1.8 : 0.7 0:1.1 1,4-Butanediol recovery rate (%) 44.8 - 1,4-Butanediol purity (%) ⁇ 98.0 - Butadiene recovery rate (%) 52.6 45.8 Butadiene purity (%) ⁇ 98.0 ⁇ 98.0
  • Examples 1 and 2 can recover lactide and butadiene with high purity and high yield, respectively, and Examples 3 and 4 can recover lactide, acrylic acid, and butadiene with high purity and high yield, respectively.
  • Examples 5 and 6 recover lactide and glycolide with a recovery rate of 81% or more, and butadiene with a recovery rate of 58% or more, and the purities of each exceed 98%, and Example 7 recovers acrylic acid, It was confirmed that glycolide and butadiene could be recovered with high purity and high yield, respectively, and Examples 8 and 9 confirmed that 1,4-butanediol and/or butadiene could be recovered with high purity and high yield, respectively.
  • Example 8 when PBAT was pyrolyzed at 250 to 300°C, it was confirmed that a lot of PBAT still remained in the residue, and the temperature was further raised to 500°C for pyrolysis to recover butadiene. Meanwhile, it was confirmed that only lactide was recovered in Comparative Example 1, only acrylic acid was recovered in Comparative Example 2, and only 1,4-butanediol was recovered in Comparative Example 3.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Sustainable Development (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Polyesters Or Polycarbonates (AREA)
  • Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)

Abstract

La présente invention concerne un procédé de préparation de butadiène comprenant une étape de préparation de butadiène par pyrolyse d'un polyester, contenant une unité de répétition dérivée de 1,4-butanediol, ou d'un mélange de polymères contenant le polyester.
PCT/KR2023/010475 2022-07-20 2023-07-20 Procédé de préparation de butadiène WO2024019560A1 (fr)

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KR1020220089693A KR20240012146A (ko) 2022-07-20 2022-07-20 락타이드, 아크릴산 및 부타디엔 제조 방법
KR10-2022-0089694 2022-07-20
KR1020220089692A KR20240012145A (ko) 2022-07-20 2022-07-20 부탄디올 및 부타디엔 제조 방법
KR20220089694 2022-07-20
KR10-2022-0089693 2022-07-20
KR10-2022-0089692 2022-07-20
KR1020220121582A KR20240042819A (ko) 2022-09-26 2022-09-26 락타이드, 글리콜라이드 및 부타디엔 제조 방법
KR10-2022-0121582 2022-09-26
KR1020220127102A KR20240047721A (ko) 2022-10-05 2022-10-05 아크릴산, 글리콜라이드 및 부타디엔 제조 방법
KR10-2022-0127102 2022-10-05
KR1020230094098A KR20240012334A (ko) 2022-07-20 2023-07-19 부타디엔 제조 방법
KR10-2023-0094098 2023-07-19

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Citations (2)

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KR20150032579A (ko) * 2012-07-16 2015-03-26 바스프 에스이 하나 이상의 분자 활성 화합물에 의해 촉매작용되는 폴리-3-하이드록시프로피오네이트의 열분해에 의한 아크릴산의 제조 방법

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